Process using metal salt-amine complex catalysts for the preparation of alpha beta-ethylenic ketones such as delta-cis-pseudo ionones

ABSTRACT

A process is provided for the preparation of Alpha , Beta ethylenic ketones by the condensation of aliphatic and cycloaliphatic tertiary acetylenic carbinols and especially for the preparation of Delta 3-cis-pseudo ionones by the condensation of dehydrolinalool and derivatives thereof with isoalkenyl ethers in the presence of metal salt-amine complex catalysts. The Delta 3-cis-pseudo ionones can be cyclized to produce the corresponding Alpha -, Beta -, and gamma -cisionones or alkyl ionones. Methods are also described for rearranging the Delta 3-cis-pseudo ionones to the normally encountered trans-pseudo ionones which in turn can be converted to the trans-ionones.

Desimone et al.

PROCESS USING METAL SALT-AMINE COMPLEX CATALYSTS FOR THE PREPARATION OF ALPHA BETA-ETHYLENIC KETONES SUCH AS DELTA-CIS-PSEUDO IONONES Inventors: Robert S. Desimone, Willingboro;

Peter S. Gradeff, Andover, both of NJ.

Assignee: Rhodia, Inc., New York, NY.

Filed: Feb. 1, 1973 Appl. No.: 328,559

US. Cl. 260/586 C; 260/593 R; 260/632 R Int. Cl. C07c 45/00 Field of Search 260/587, 593 R, 586 R,

References Cited UNITED STATES PATENTS 4/1962 Riehen et al 260/587 7/1969 Riehen et al. 260/593 R [451 May 27, 1975 3,574,715 4/1971 Riehen et a1 260/593 R FOREIGN PATENTS OR APPLICATIONS 666,786 7/1963 Canada 260/593 R Primary Examiner-Bernard Helfin Assistant ExaminerJames H. Reamer [57] ABSTRACT A process is provided for the preparation of a, B-ethylenic ketones by the condensation of aliphatic and cycloaliphatic tertiary acetylenic carbinols and especially for the preparation of A -cispseudo ionones by the condensation of dehydrolinalool and derivatives thereof with isoalkenyl ethers in the presence of metal salt-amine complex catalysts. The A -cis-pseudo ionones can be cyclized to produce the corresponding 01-, 8-, and y-cis-ionones or alkyl ionones. Methods are also described for rearranging the A -cis-pseudo ionones to the normally encountered trans-pseudo ionones which in turn can be converted to the transionones.

25 Claims, No D'rawings PROCESS USING METAL SALT-AMINE COMPLEX CATALYSTS FOR THE PREPARATION OF ALPHA BETA-ETHYLENIC KETONES SUCH AS DELTA-CIS-PSEUDO IONONES lonones occupy a prominent place in perfumery. It would be hard today to find a perfume composition that does not contain an ionone. More than one hundred ionones are known; the most widely used ones are ,B-ionone, a-ionone, the methyl ionones, and the irones. B-ionone also is a principal intermediate in the preparation of synthetic Vitamin A.

The importance of the ionones is reflected in the ef forts reported in the literature to find suitable ways for their manufacture. All of the commercial methods start from citral or dehydrolinalool, and proceed via the pseudo ionones to the ionones. For example, citral is condensed with acetone or methyl ethyl ketone, and the pseudo ionone cyclized to ionone. Dehydrolinalool is reacted with ethyl acetoacetate by Carrolls synthesis to pseudo ionone, followed by cyclization. Condensation of citral with 2-ethoxy-propene yields the triethoxy derivative of pseudo ionone which leads to the pseudo ionone (U.S. Pat. No. 3,109,861, dated Nov. 5, 1963, to Guex, Marbet and Montavon). Pseudo ionone also is prepared from dehydrolinalool and methyl acetoacetate or diketene. The rearrangement of dehydrolinalool acetate to enol acetate of citral followed by reaction with acetone and the rearrangement of the allenic ketone formed by condensation of a ketal or an enol ether and dehydrolinalool (U.S. Pat. No. 3,029,287, dated Apr. 10, 1962, to Marbet and Saucy) both yield pseudo ionone.

B-lonone, for instance, is obtained by cyclization of pseudo ionone under the influenceof acid:

One should notice that in the case of both ,B-ionone and pseudo ionone, the configuration of the A double bond conjugated to the carbonyl is trans. This is the normal form. The cis-A configuration of pseudo ionone has been postulated as theoretically possible, but not favored, and unstable. In fact, efforts to prepare the cisisomer have all failed (J. Chem. Soc. 1965 5528). Two cis-isomers are possible, depending on the configuration at the A double bond:

Cis-A, Trans-A D HC CH -H CECMgBr CH MgBr The cis-aor B-ionone can also be obtained by ultraviolet irradiation of aor B-trans-ionones.

It is believed that the cis-B-ionone is in equilbrium with the pyran structure:

This is discussed in an article published in J. Am. Chem. Soc. 88 619-20 (1966). Most recently, Martel] et al. (J. Org. Chem. 37 2992, (1972)) have also demonstrated that A -cis ionone exists in equilibrium with the pyran form. The preparation of cis-oz-ionone from the transiomer by irradiation is described by Buchi and Wang in Helv. Chem. Acta 1339 (1955). However, since the cis-B-ionone apparently also is present in the open chain structure at least to some extent, and the equilibrium is such that the mixture behaves as though it were all in the open chain structure, it is unnecessary to consider the pyran structure in the specification and claims of this application, and it will not be referred to further.

It has now been discovered. that the cis-A -pseudo ionones, compounds previously unknown and considered to be too unstable to exist, can be prepared from dehydrolinalool and its homologues by reaction with alkoxy propenes or butenes in the presence of a metal saltamine complex as a catalyst at a temperature within the range from about 80 to about 150C. Furthermore, it appears that of the two possible cis-A -isomers, cis-A cis-A and cis-A -trans-A only one is present, and interpretation of some analytical data points to the cis- N-trans-A isomer.

It is quite surprising that the cis-A isomer is obtained in this process, since all other known processes (such as that of US. Pat. No. 3,029,287) starting from dehydrolinalool and its homologues lead to the trans-A pseudo ionones. It appears that the metal salt-amine complex is primarily responsible for this remarkable result, and the metal salt-amine complex also makes possible the obtention of the cis-A -isomer in a one step process.

The cis-A -pseudo ionone can be converted to the cis-ionone which exists in equilibrium with the a-pyran form, and this can be isomerized to the trans-ionone. The cis-A -pseudo ionone can also be isomerized to the trans-A -pseudo ionone, and this can be converted to the trans-ionone.

Accordingly, in the process of the instant invention, one of the class of dehydrolinalool and its derivatives thereof is reacted with an isoalkenyl ether at a temperature within the range from about 80 to about 150C. in the presence of a metal salt-amine complex to produce the corresponding A -cis pseudo-ionone or A -cispseudo methyl ionone. The isoalkenyl group of the ether has from three to four carbon atoms, and the class includes isopropenyl and isobutenyl lower alkyl ethers. The substituent groups of the dehydrolinalool include alkyl, alkenyl, cycloalkyl and cycloalkenyl, the alkyl and alkenyl groups having from one to about thirty carbon atoms, and the cycloalkyl and cycloalkenyl having from three to about thirty carbon atoms. The lower alkyl and alkenyl homologues, the alkyl having from one to four carbon atoms, and the alkenyl from two to four carbon atoms, are preferred. While some trans-A -isomer may be obtained, the cis-A isomer is produced in predominant proportion.

The cis-A -pseudo ionones offer a convenient and direct route for preparation of the corresponding cisionones and cis-methyl ionones.

The cis-A -pseudo ionones can be isomerized to the trans-A -isomers, which lead to the corresponding known ionones and methyl ionones.

The process of the invention is applicable to any tertiary acetylenic carbinol having the general formula:

wherein:

a. R is selected from the group consisting of:

wherein R R and R are selected from the group consisting of hydrogen, lower alkyl and lower alkenyl, having from one to about four carbon atoms;

b. R" is selected from the group consisting of lower alkyl and lower alkenyl, having from one to about four carbon atoms.

In the case where the isoalkenyl ether is an isopropenyl ether, the condensation reaction of the invention proceeds as represented by Scheme 1 to produce an a, B-ethylenic ketone:

alkenyl ether. the condensation reaction proceeds as shown in Scheme ll, to produce two or more isomeric a, B-ethylenic ketones:

5 6 SCHEME :1 Continued V i i i RandR =loweralkyl R' 'C:CH C:C C-CH2 R having from one to four 5 carbon atoms or, B-ethylenic ketone II 5 OH V The class of tertiary acetylenic alcohols having a R c CH dehydrolinalool structure is an example. The dehy- ---OR drolinalools to which the process of the invention is ap- R" I plicable have the general formula:

Isobutenyl ether 7 7 l5 H H R5 wherein R,, R R and R are selected from the rou I I l 20 g p R c CH -'c c c 3n consisting oflower alkyl and lower alkenyl, as indicated 1 above, having up to about four carbon atoms.

In the case where the isoalkenyl ether is an isopropenyl ether, the application to the class of dehy- 25 drolinalools of the reactions of the invention results in a cis-A -pseudo ionone, and can be represented by Scheme ill:

zv, li -ethylenic kclone I SCHEME III R lower alkyl having from one to our carbon atoms Reaction (2. Condensation Isopropenyl ether Dehydrolinalool or Derivative Cis- A pseudo ionone Trans -A '-pseud0 ionone Scheme III Continued Reaction to) Cyclization CisA -pseud0 ionone C201 8-, -y) ionone When the isoalkenyl ether is an isobutenyl or higher alkenyl ether, the application to the class of dehydrolinalools of the reactions of the invention results in two or more isomeric cis-A -pseudo ionones, and can be represented by Scheme IV:

SCHEME IV R and R lower alkyl having from one to four carbon atoms Reaction (a! Condensation Isobutenyl ether Dehydrolinalool or Homologue Cis-M-normal alky.

Cis-A -iso alkyl pseudo ionone pseudo ionone Reaction (b) Isomcrization to trans-N-isomer Qs-A -norma1 alkyl pseudo ionone pseudo ionone pseudo ionone Cis-iso alkyl ionone While the process in accordance with the invention is operative with lower isoalkenyl ethers in which R is higher than methyl, such as ethyl, propyl, and isobutyl, the process is of major commercial interest when R is methyl.

The terms cis-A -pseudo ionone," cis-N-iso alkyl pseudo ionone and cis-A -normal alkyl pseudo ionone" are used generically herein to refer to compounds of the formulae represented above. Likewise, the terms cis-ionone" and cis-alkyl ionone" are used generically to refer to cis-iononcs of the formulae represented above. However, it will be apparent that isopropenyl ethers produce pseudo ionones, and that isobutenyl ethers produce cis-Aalkyl pseudo ionones. The cisalkyl-pseudo ionones exist in iso and normal forms. Upon cyclization, both pseudo ionones and alkyl pseudo ionones produce mixtures of cis-w. B-, and y-ionones and cis-alkyl ionones.

C i s -normal alkyl ionone It will of course be understood that when R and R are both lower alkyl, the a-ionone isomers do not exist.

During the coupling ofthe isoalkenyl ether with the tertiary acetylenic carbinol, the R substituent of the isoalkenyl ether is converted to the corresponding alcohol which is normally trapped by the excess of isoalkenyl ether.

When R,, R and R arehydrogen and R is methyl, the acetylenic alcohol is dehydrolinalool. Condensation of dehydrolinalool with an isopropenyl ether produces cis-A -pseudo ionone, and the condensation of dehydrolinalool with isobutenyl ethers produces cis-A methyl pseudo ionone in both. iso and normal forms.

Derivatives and homologues of dehydrolinalool in like manner give the corresponding ionones and cis-A methyl pseudo ionones in iso and normal forms.

The process of the invention is applicable, for instance, to the following tertiary acetylenic carbinols:

- Continued 41 X4 10 1? X- O I k KM l \so-c fi H I In the case when R and R are both alkyl, for instance,

I OH l H k H C H the corresponding cis-ionones are only B- and 'y-:

4 r, and

These lead to preparation of the following exemplary 40 cis-a-ionones, when an isopropenyl ether is used as a reagent, in Scheme 1:

These lead to preparation of the following exemplary cis-iso-methyl-a-ionones, when the corresponding isobutenyl ether is used as a reagent, in Scheme ll:

Continued The process of the invention is also applicable, for instance, to the following cases:

The metal salt-amine complex has an unknown structure, but can be defined by the empirical formula:

wherein:

a. MY is the metal salt, which is capable of complexing with amines, M representing the metal and Y the anion of the salt. Exemplary salts are those of copper, chromium and silver.

b. R,, R and R are selected from the group consisting of:

i. monovalent hydrocarbon groups having from one to about thirty carbon atoms (in which case the compounds are aliphatic hydrocarbon amines);

ii. bivalent hydrocarbon groups (two of R R and R being taken together to form a cyclic ring) which may include hetero atoms such as nitrogen, oxygen, and sulfur, as in morpholine and thiazole (in which case the compounds are cycloaliphatic hydrocarbon amines, monocarbocyclic aromatic amines, and heterocyclic amines);

iii. trivalent hydrocarbon groups (the three R R and R being taken together), as in pyridine;

iv. hydrogen.

c. n is the number of amine groups in the complex and is within the range from about 0.01 to about 50, preferably from 1 to 6, and is not necessarily representative of a molar relationship.

It will be understood that the number of metal ions M and anions Y in the metal salt is balanced according to the valence of each.

Exemplary amines are methyl amine, butyl amine, decyl amine, diethyl amine, dipropyl amine, dibutyl amine, dioctyl amine, aniline, p-toluidine, m-toluidine, trimethylamine, triethylamine, ethyl dimethylamine, decyl dipropyl amine, N-methyl aniline, cyclohexyl amine, cyclopentylamine, methyl cyclohexyl amine, morpholine, pyridine, pyrazine, piperidine, pyrimidine, quinoline, isoquinoline, thiazole, triazole, oxazole, and pyrrole.

The catalyst is prepared by reaction of the amine with a compound of the metal. The liquid amine can serve as the reaction medium. Water can also be added to dissolve the metal compound, if it is water-soluble. A lower aliphatic alcohol can also serve as a solvent.

Any metal salts can be used. The effective available salts are usually those in which the anion Y is chloride, bromide, iodide, nitrate, sulfate.

The effectiveness of the metal amine-salt complex is surprising, since the amine alone has no catalytic effect, and neither do most of the metal salts. Even if the metal salt has some catalytic effect, such as copper sulfate, the effect can be enhanced greatly by the amine.

The amount of the amine is in no way critical, and is not stoichiometric, although a complex is definitely present. This apparently is due to the fact that excess metal salt or amine that may not be complexed and may exist as the metal salt or amine may be present. Hence, the catalyst can contain an amount of nitrogen within the range from about 1 to about 30%. For optimum effect, however, a molar proportion where n is l to 4 is preferred.

The amount of catalyst can be rather small. An amount as low as 1% is effective, but better results are obtained with amounts within the range from about 2% to' about While larger amounts than 5% can be used, up to approximately there seems to be no advantage commensurate with the larger amount of catalyst employed.

The reaction time is normally within the range from about 0.2 hour to about 3 days, depending upon the reagents, the degree of agitation, temperature and the amount of catalyst present. Usually, the reaction is complete within about 2 to about 40 hours.

The reaction temperature is also quite critical. The reaction proceeds at temperatures from about 80 to about 150C., preferably from 85 to 120C. At temperatures below 80C., the reaction does not proceed at a measurably practical rate. At temperatures in excess of 125C., only the trans-A -isomer is produced, and side reactions tend to reduce the yield even of the trans-isomer.

Because of the low boiling point of the isoalkenyl ether, the reaction is carried out in a closed vessel, so as to retain the isoalkenyl ether within the reaction mixture. Good agitation is desirable.

Surprisingly, the reaction proceeds better and in a higher yield in the absence of a so1vent.ln the presence of a solvent, even in as small an amount as 5% by weight of thereagents (dehydrolinalool and isoalkenyl ether), some reaction takes place, but the yield is reduced.

Thus, thecatalyst seems to require a high concentration of the reagents. Effectiveness is markedly reduced when the reagents are diluted by an external solvent, even in small amounts.

The cis-A -pseudo ionone after isolation from the reaction mixture can be cyclized to the ionone or alkyl ionone using an acidic cyclizing reagent. This reaction is conventional, and proceeds in the usual manner, under normal operating conditions, using conventional acids, for example, phosphoric acid in the presence of a suitable solvent, and heating, or a sulfuric acid-acetic acid mixture at low temperature.

It is also possible to isomerize the cis-A -pseudo ionone to the corresponding trans-A -pseudo ionone by irradiation with ultraviolet light or by treatment with an isomerizing reagent, such as iodine. The isomerization can alsobe accomplished upon heating for extended periods. The isomerization takes place at room temperature, although elevated temperatures up to about 150C. can be employed. Very small amounts of reagent are effective. As little as 0.2% reagent can be used. lsomerization is complete when amounts within the range from about 0.2 to 0.4% reagent is used. Amounts in excess of this, up to about 10%, can be employed, but no advantage appears to be obtained in doing so.

A preferred isomerizing reagent is an elemental halogen, such as bromine or iodine. lodine is best used in solution in an inert solvent for iodine, such as isopropyl ether or ethyl ether, to facilitate contact with the cispseudo ionone or alkyl pseudo ionone.

In general, any acid or base or acidic or basic salt can be used as the isomerizing reagent, to effect isomerization of cis-A to trans-A -pseudo ionone; acids include sulfonic acids such as paratoluene sulfonic acid, and octane sulfonic acid; carboxylic acids such as formic acid, acetic acid, trichloroacetic acid and propionic acid; inorganic acids such as nitric acid, phosphoric acid, sulfuric acid, and hydrochloric acid; and Lewis acids, such as BF Bases include sodium hydroxide, potassium hydroxide, and ammonium hydroxide, and silver nitrate is an example of a salt.

Isomerization also can be effected by irradiation with ultraviolet light. The isomerization proceeds at room temperature under such irradiation and in a relatively short time, from 0.2 hour up to 10 hours.

Heating at an elevated temperature within the range from about 50 to about 150C. can also isomerize the cis-A to trans-A -pseudo ionone. Heating is sufficient by itself, although addition of an isomerizing reagent or irradiation with ultraviolet light may expedite the isomerization reaction.

By direct cyclization of the cis-A -pseudo ionone with strong acids, a mixture containing large amounts of cis- (B-, ,8-, and 'y-) ionone can be obtained. The cis-(a-, 3-, and y-) ionones have quite distinct olfactory characteristics, different from trans-a-, 3-, and y-ionones, and are useful as perfume agents.

The following Examples in the opinion of the inventors represent preferred embodiments of the invention:

EXAMPLE 1 Anhydrous cupric sulfate (6.0 grams) was dissolved in water and 27.7 grams of quinoline was added, with immediate formation of a light green precipitate. Methanol (100 ml) was then added, the slurry filtered, the filter cake washed with methanol, and the light green solid allowed to air dry. Analysis of the solid showed 17.6% Cu, 6.81% S, 48.99% carbon, 3.81% hydrogen, and 6.50% nitrogen.

Dehydrolinalool (15.2 grams, 0.1 mol) and 2- methoxy propene (21.6 grams, 0.3 mol) were combined in a pressureresisting bottle with 0.3 gram of the above catalyst. A magnetic stirring bar was added, and the bottle closed and immersed in an oil bath, heated to C. for 4.2 hours, The resulting oily mixture was washed with water. The low boiling fraction was distilled to 60C. at 44 mm Hg, and the remaining brown oil flash-distilled at 40 to 220C. head temperature, 1.2 to 1.5 mm Hg, to give 1.1 grams of residue and 17.9 grams of distillate.

The distillate contained 0.48 grams of recovered dehydrolinalool, 15.0 grams of cis-A -pseudo ionone, and 1.0 grams of trans-A -pseudo ionone.

EXAMPLE 2 Into a flask containing 3.0 grams of anhydrous copper sulfate was added 30 grams of diethylamine with stirring. After stirring the mixture four days at room temperature, the solids were filtered, washed with ethyl acetate and air-dried to give a blue powder. Analysis of the powder showed 8.15% H. 33.07% C, 9.41% N, and 25.9% Cu.

Dehydrolinalool (15.2 grams, 0.1 mol) and 2- methoxy-propene (21.6 grams, 0.3 mol) were combined in a pressureresisting glass bottle with 0.3 gram of the above catalyst, a magnetic stirring bar was added, and the bottle closed and immersed in an oil bath heated at 90C. for 3.75 hours. The brown essentially homogeneous mixture was washed with water. The low boiling fraction was removed under aspirator vacuum, and the remaining oil was flash-distilled at a head temperature of 40 to 174C, pot temperature 80 to 200C., 1.0 mm Hg, to give 14.9 grams of distillate and 4.3 grams of residue.

The distillate contained 0.8 gram of recovered dehydrolinalool, 3.8 grams of cis-A -pseudo ionone, and 5.3 grams of trans-A -pseudo ionone.

EXAMPLE 3 Triethylamine (30 grams) and 3.0 grams of anhydrous cupric sulfate were combined in a pressure vessel, and a magnetic stirring bar added. The slurry was stirred at 90C. for 21.5 hours, whereupon the light green solids were filtered, and the filter cake washed with ethyl acetate prior to air drying. The catalyst showed 3.14% nitrogen, 15.42% carbon, and 4.44% hydrogen on analysis.

Dehydrolinalool (15.2 grams, 0.1 mol) and 2- methoxy propene (21.6 grams, 0.3 mol) were combined in a pressure bottle with 0.3 grams of the above catalyst, a magnetic stirring bar was added, and the bottle closed and immersed in an oil bath with stirring for 2.5 hours at 90C. The essentially homogeneous reaction mixture was cooled, and washed with water. The low boiling fraction was removed under aspirator vacuum, and the remaining oil flash-distilled at 40 to 135C. head temperature, 80 to 190 C. pot temperature, 1.1 to 1.5 mm Hg, to give 18.5 grams distillate and 0.7 gram of residue.

The distillate contained 1.7 gram of recovered dehydrolinalool, and 15.72 g of condensation product. The direct yield was 82.0%, and the true yield was 92.4%.

EXAMPLE 4 Copper sulfate (6.0 grams) was dissolved in water and 16.8 grams of pyridine was added dropwise, with agitation and cooling. After the addition was complete, the mixture was stirred for 1 hour, and ethanol added. The sky-blue precipitate was filtered, washed with ethanol. and air dried to a constant weight. Elemental analysis showed 10.35% nitrogen, 33.68% carbon, 3.97% hydrogen, and 17.9% copper.

Dehydrolinalool (15.2 grams, 0.1 mol) and 2 methoxy propene (21.6 grams, 0.3 mol) were combined in a pressureresisting glass bottle with 0.3 gram of the above catalyst, a magnetic stirring bar was added, and the bottle closed and immersed in an oil bath with stirring for 17.5 hours at 90C. The essentially homogeneous reaction mixture was cooled and washed with water. The low boiling fraction was removed under aspirator vacuum, and the remaining oil flash-distilled at 75 to 142C. head temperature, 125 to 163C. pot temperature, 0.5 to 3.9 mm Hg, to give 18.2 grams of distillate and 1.6 gram of residue.

The distillate contained 0.8 gram of recovered dehydrolinalool, 12.1 gram of cis-A -pseudo ionone. and 3.2 grams trans-A -pseudo ionone.

EXAMPLE 5' To 6.0 grams of cupric sulfate dissolved in water was added 16.8 grams of pyridine, dropwise with agitation, and the resulting mixture allowed to stir for one hour at ambient temperature. The light blue solid was filtered, washed with ethyl acetate and air dried overnight. Elemental analysis showed 4.55% nitrogen, 20.86% carbon, 2.75% hydrogen, while wet analysis showed 25.6% Cu, and 6.3% water.

Dehydrolinalool (15.2 grams, 0.1 mol) and 2- methoxy propene (21.6 grams, 0.3 mol) were combined in a pressure bottle with 0.3 grams of the above catalyst, a magnetic stirring bar was added, and the bottle closed and immersed in an oil bath with stirring for 1 hour and 50 minutes at C. The essentially homogeneous reaction mixture was cooled, and washed with water. The low boiling fraction was removed under aspirator vacuum, and the remaining oil flash-distilled at 30 to 121C. head temperature, to C. pot temperature, 0.6 to 1.1 mm Hg, to give 16.0 grams of distillate and 5.7v grams of residue.

The distillate contained 6.7 grams of cis-A -ionone and 5.6 grams of trans-A pserudo ionone.

EXAMPLE 6 To 4.0 grams of Cr(NO ]l .9H O in 50 ml of hot methanol was added 4.8 grams of pyridine. The dark blue solution was placed under 30 mm Hg vacuum for 68 hours at room temperature, to give 4.9 grams of gun-grey crystals. Elemental analysis showed 13.40% nitrogen, 41.88% carbon, 3.62% hydrogen and 8.14% chromium.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 grams of the above catalyst in a glass-lined pressure vessel. A magnetic stirring bar was added, and the mixture stirred at 90C. for 2 hours, at which time the salmon-brown mixture was filtered, washed with water, and vacuum evaporated at 40 mm Hg 60C. Flash distillation of the remaining brown oil at 53 to 154C. head temperature, 70 to C. pot temperature, gave 14.9 grams of distillate and 0.7 grams of residue at}0.8 mtriHg.

Gas-liquid chromatographic analysis of the distillate showed 6.12 grams of recovered dehydrolinalool, 6.85 grams of cis-A -pseudo ionone, and 1.49 grams of trans-A -pseudo ionone.

EXAMPLE 7 To 4.0 grams of CR(NO .9H O dissolved in 50 ml of hot methanol was added 4. 8 grams of pyridine. The dark blue solution was placed under 40 mm Hg for 68 hours at room temperature to give 4.9 grams of gungrey crystals. Elemental analysis showed 13.40% nitrogen, 41 .88% carbon, 3.62% hydrogen and 8.14% chromium.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a glass-lined pressure vessel. A magnetic stirring bar was added, and the mixture stirred at 90C. for 18 hours, after which the mixture was filtered, washed with H 0, and vacuum-evaporated at 40 mm Hg, 60C. Flash distillation of the remaining brown oil at 54 to 135C. vapor temperature, 65 to 200C. pot temperature, 0.8 mm Hg, afforded 16.6 grams of distillate and 0.6 gram of residue. Gas-liquid chromatographic analysis of the distillate showed 8.03 grams of recovered dehydrolinalool, and 8.22 grams of condensation product.

EXAMPLE 8 To 6.0 grams of cupric sulfate dissolved in 20 ml of water was added 20 grams of aniline, dropwise with stirring. The resulting yellow solid was filtered, washed quickly with methanol, and air dried to constant weight. Elemental analysis showed the catalyst to contain 7.62% nitrogen, 3.92% hydrogen, 41.59% carbon, while wet analysis showed 18.4% copper.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a glass-lined pressure vessel. A magnetic stirring bar was added, and the mixture heated at 90C. with stirring for 4.8 hours. The reaction mixture was cooled, washed three times with equal volumes of water (H O washes cross-extracted with cyclohexane), and the combined organic phases dried over sodium sulfate prior to vacuum stripping of solvent. Flash distillation at 0.4 to 1.0 mm Hg, 50 to 150C. head temperature, and 85 to 200C. pot temperature, gave 17.3 grams of distillate and 2.5 grams of residue.

The distillate contained 0.42 gram of dehydrolinalool, 10.8 grams of cis-A -pseudo ionone and 3.8 grams of trans-A -pseudo ionone.

EXAMPLE 9 To 3.6 grams of cupric chloride dissolved in 20 ml of water was added 16.8 of pyridine, dropwise with agitation, with immediate formation of a blue color. Methanol was added to precipitate the complex, which was filtered, washed three times with methanol, and air dried to a light blue powder. The catalyst was found to contain 13.40% nitrogen, 41.88% carbon, 3.62% hydrogen, and 23.2% copper, upon elemental analysis.

Dehydrolinalool (15.2 grams) was combined with 21.6 grams of 2-methoxy propene and 0.3 gram of the above catalyst. A magnetic stirring bar was added, and the mixture stirred at 90C. for 54.5 hours at which time the essentially homogeneous brown solution was cooled, and washed three times with equal volumes of water. The water washes were cross-extracted with cyclohexane, and the combined organic phases dried over sodium sulfate, and the solvent removed under aspirator vacuum. Flash distillation of the remaining brown oil at 0.8 mm Hg, 50 to 124C. head temperature, 57 to 140C. pot temperature, gave 15.5 grams of distillate and 2.7 grams of residue.

Gas chromatographic analysis of the distillate showed 11.1 grams dehydrolinalool, 1.74 gram cis-A pseudo ionone, and 0.12 gram trans-A -pseudo ionone.

EXAMPLE 10 A solution of 3.0 grams of CuSeO, in 5 ml of hot water was combined with 8 ml of methanol, at which point aprecipitate was obtained. Pyridine (4.8 grams) was then added, with heating to obtain a dark blue solution, to which was added, in succession, 200 mls of methanol, and 500 mls of acetone. The resulting flocculent pale blue precipitate was filtered, and washed with methanol and thenether prior to air drying overnight, yielding a pale aqua blue powder. The powder showed 5.82% nitrogen, 25.80% carbon, 2.94% hydrogen, and 20.4% copper on elemental analysis.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst. A magnetic stirring bar was added, and the mixture heated with stirring for 49.5 hours at 90C The mixture was cooled, washed with water (cross extracted with cyclohexane) and dried over sodium sulfate prior to removal of low boilers under aspirator vacuum. The resulting oil was flash-distilled at 0.8 mm Hg, 50 to 181C. head temperature, 56 to 220C. pot temperature, to yield 13.0 grams of distillate and 1.4 gram of residue.

The distillate by gas-liquid chromatographic analysis was found to contain 11.0 grams of dehydrolinalool, 0.94 gram of cis-A -pseudo ionone, and 0.27 gram of trans-A -pseudo ionone. The direct yield was 6.6%, and the true yield 23.0%.

EXAMPLE 1 1 To 6.5 grams of Cu(NO .31-l O in 20 ml of methanol was added 16.8 grams of pyridine. The resulting deep violet blue precipitate was washed with methanol, and air dried overnight. Elemental analysis showed 11.66% copper, 16.75% nitrogen, 4.13% hydrogen, and 47.87% carbon.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of methoxy propene and 0.3 gram of the above catalyst in a glass-lined pressure vessel. A magnetic stirring bar was added, and the mixture stirred at C. for 3.2 hours. After cooling, the turbid brown solution was washed with water (cross-extracted with cyclohexane) and dried over sodium sulfate prior to removal of low boilers under aspirator vacuum. Flash distillation as in Example 10 gave 17.6 grams of distillate and 1.5 gram of residue.

The distillate by gas-liquid chromatographic analysis was found to'contain 4.47 grams of dehydrolinalool, 1 1.16 grams of cis-A -pseudo ionone, and 1.33 gram of trans-A -pseudo ionone.

EXAMPLE 12 To 3.6 grams of cupric chloride dissolved in 20 ml of water was added 16.8 grams of pyridine, dropwise with stirring. The resulting blue solution was combined with methanol, to precipitate a blue solid, which was filtered, washed three times with methanol and air dried to a constant weight. The light blue powder was shown to contain 23.2% copper, 13.40% nitrogen, 41:88% carbon, and 3.62% hydrogen upon elemental analysis.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a pressure-resisting glass-lined vessel. A magnetic stirring bar was added, and the mixture stirred at C. for 28.3 hours. The turbid dark brown solution was washed with water, dried over Na SO and flash-distilled at 53 to 198C. head temperature, 68 to 212C. pot temperature, 0.8 mm Hg, to give 15.6 grams of distillate and 0.8 gram of residue.

- The distillate contained 1 1.8 grams of dehydrolinalool, 1.56 gram of cis-A -pseudo ionone and 0.14 gram of trans-A -pseudo ionone.

EXAMPLE 13 To 3.0 grams of Cu(BF in 15 ml of hot methanol was added 9.6 grams of pyridine. Upon cooling, a precipitate was obtained, which was washed with metha-' nol, then with ether and air dried to give 1.7 gram of a violet micro-crystalline powder. The catalyst contained 10.8% copper, 10.07% nitrogen, 3.75% boron, 43.30% carbon and 3.79% hydrogen, upon elemental analysis.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a glass-lined pressure-resisting vessel. A magnetic stirring bar was added, and the mixture heated at 90C. with stirring for 19.8 hours. The resulting turbid dark brown mixture was filtered, washed with water (cyclohexane used to cross extract and rinse) and low boilers removed under aspirator vacuum. Flash distillation at 40 to 150C. head temperature, 60 to 190C. pot temperature, 0.5 mm Hg gave 19.2 grams of distillate and 1.8 gram of residue.

Gas'liquid chromatographic analysis showed the distillate to contain 11.46 grams of dehydrolinalool and 2.63 grams of condensation product.

EXAMPLE 14 To 6.0 grams of AgNO in ml of water was added 22.4 grams of pyridine, dropwise with stirring. The resulting clear solution was placed under 40 mm vacuum over a three-day period, to give white crystals. The crystals were washed with ethyl acetate, and air dried to a constant weight, 11 grams. Elemental analysis of the crystals showed 26.67% Ag, 36.15% C, 12.94% N, and 2.99% H.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a pressure-resisting glass-lined vessel. A magnetic stirring bar was added, and the mixture heated at 90C. with stirring for 16.1 hours. During the initial phase of heating, the reaction mixture was homogeneous. The resulting turbid, black mixture was filtered, washed with water and low boilers removed under aspirator vacuum. Flash distillation at 50 to 120C. head temperature, 65 to 160C. pot temperature and 0.5 to 0.2 mm Hg gave 15.8 grams of distillate and 1.0 gram of residue.

The distillate contained 1 1.04 grams of dehydrolinalool, and 5.3 grams of condensation product.

EXAMPLE 15 To 6.0 grams of CuSO, dissolved in water was added 16.8 grams of pyridine, dropwise with agitation, and cooling. After stirring for 1 hour, ethanol was added to precipitate the complex, which was filtered and washed with ethanol. Air drying gave 8.2 grams of a sky-blue powder, which showed 17.9% copper, 9.38% sulfur, 10.35% nitrogen, 3.97% hydrogen and 33.68% carbon, on elemental analysis.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy-2-butene and 0.3 gram of the above catalyst in a pressure-resisting glass-lined vessel. A magnetic stirring bar was added, and the mixture stirred at 83 to 92C. for 17 hours. After cooling, the resulting turbid, brown solution was filtered, washed with water (cross-extracted with cyclohexane) and low boilers removed under aspirator vacuum. Flash distillation of the remaining brown oil at 48 to 205C. head temperature, 51 to 225C. pot temperature and 0.8 mm Hg gave 13.5 grams of distillate and 1.2 gram of residue.

The distillate contained 3.77 grams of dehydrolinalool, and 4.77 grams of a mixture of 3-methyl cis-A' pseudo ionone, l-methyl-cis-A pseudo ionone and mixed trans-A -methy1 pseudo ionones.

EXAMPLE 16 To 3.0 grams of pulverized CuSO was added 30 grams of n-propylamine, and the mixture stirred at ambient temperature for 4 days. After filtration, the solids were washed with ethyl acetate and air dried to constant weight, to give 7.9 grams of dark blue crystals which contained 33.07% C. 9.41% N, and 8.15% H.

Dehydrolinalool (15.2 grams) was combined with 21.6 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a pressure-resisting glass-lined vessel. A magnetic stirring bar was added, and the mixture stirred for 12.8 hours at C. The dark brown turbid reaction mixture was filtered, washed with water, and the washings cross-extracted with cyclohexane. The combined organic phases were dried over sodium sulfate, and the low boilers removed under aspirator vacuum. Flash distillation of the remaining brown oil at 40 to C. head temperature, 80 to 190C. pot temperature, and 0.7 to 1 mm Hg, gave 15.2 grams of distillate and 1.5 gram of residue.

The distillate contained 8.4 grams of dehydrolinalool, 5.1 grams of cis-A -pseudo ionone and 0.5 gram of trans-A --pseudo ionones.

EXAMPLE 17 To 6.0 grams of cupric sulfate dissolved in 20 ml of water was added 20 grams of aniline, dropwise with stirring. The yellow solid was filtered, washedlquickly with methanol, and air dried to constant weight. Elemental analysis showed the catalyst to contain 7.62% nitrogen, 3.92% hydrogen, and 41.59% carbon, while wet analysis showed 18.4% copper.

Dehydrolinalool (15.2 grams) was combined with 21.4 grams of 2-methoxy propene and 0.3 gram of the above catalyst in a glass-lined pressure vessel. A mag netic stirring bar was added, and the mixture heated at 90C. with stirring for 4.8 hours. The reaction mixture was cooled, washed three times with equal volumes of water (H O washes, cross-extracted with cyclohexane) and the combined organic phases dried over sodium sulfate prior to vacuum stripping of solvent. Flash distillation at 0.4 to 1.0 mm Hg, 50 to 150C. head temperature and 85 to 200C. pot temperature gave 18.9 grams of distillate and 1.2 gram of residue.

The distillate contained 0.3 gram of dehydrolinalool, 13.8 grams of cis-A -pseudo ionone and 1.6 gram of trans-A -pseudo ionone. An 87.2% direct yield and 88.9% true yield were obtained.

EXAMPLE 1s Cis-A -Pseudo ionone was isomerized to trans-A pseudo ionone. The cisA -pseudo ionone (86.2% cis, 5.2% trans) 10 g, and 0.4 g of a 5% solution of iodine in isopropyl ether were mixed, and the mixture allowed to stand for 2.1 hours at room temperature. The isopropyl ether was then removed under aspirator suction, and the oil flash-distilled at 0.3 and 1 mm, head temperature 70 to C, pot temperature 96 to 168C, to give 9.2 g distillate and 0.8 g residue. Gas-liquid chromatographic analysis of the distillate, as compared to the starting material, showed nearly complete rearrangement of the cis-A -pseudo ionone to trans-A pseudo ionone, as the following analysis shows:

EXAMPLE l9 Cyclization of Cis-A -Pseudo lonone to a -lonone Into a three-necked 150 ml flask equipped with a mechanical stirrer, condenser, static nitrogen head and thermometer was charged 15 g of cis-A -pseudo ionone (86.5% cis-A -pseudo ionone, 5.8% trans-A -pseudo ionone), 15 g of cyclohexane and 750 mg of 85% phosphoric acid. The mixture was heated to reflux (81 to 84C.) for a total of 14 hours, and after cooling washed with water (200 ml) and saturated aqueous sodium bicarbonate (100 ml). The solution was then dried over Na SO the solvent removed under aspirator vacuum and the remaining oil flash-distilled at 1.2 to 1.5 mm Hg, 66 to 110C. head temperature, 87 to 160C. pot temperature, to give 7.1 g of light yellow oil containing 10.5% cis-B-ionone, 2.4% cis-a-ionone, 40.8% trans-aionone and 12.8% trans-B-ionone.

EXAMPLE 20 A 5.0 g portion of cis-A -pseudo ionone (86.2% cis- A 5.2% trans-A was isomerized to the trans-isomer by mixing with 0.1 g of a solution of 0.25 g H SO in 5 g of methanol and allowing to stand at room temperature for 3 hours. The mixture was quenched in 40 ml of saturated sodium carbonate solution, and the organic phase taken up in benzene and washed with water. The organic phase was concentrated on aspirator vacuum and then flash-distilled at 0.2 to 0.5 mm Hg, 76 to 156C. head temperature, 85 to 205C. pot temperature, to give 0.5 g residue and 3.7 g distillate (9.3% cis-A 86.6% trans-A corresponding to a direct yield of 68.3%, true yield 74.2%.

EXAMPLE 21 Elapsed Reaction Relative Relative Time (Hrs.) 70 Cis 7r Trans EXAMPLE 22 One g cis-A -pseudo ionone was isomerized to the trans-isomer by heating with 1.5 g HOAc at 62 to 68C. for 12.5 hours. Gas-liquid chromatographic analysis at the elapsed reaction times indicated showed the isomer distribution below:

Elapsed Reaction Relative Relative Time (Hrs.) 7r Cis 7: Trans EXAMPLE 23 One g of 5,10-dimethyl-cis-A -5,9-undecatrien-2-one was isomerized to the trans-isomer using 1 g of a solution of 1 g NaOH in 25 ml of MeOH. The mixture was allowed to stand at ambient temperature for 5.25 hours. Gas-liquid chromatographic analysis at the elapsed reaction times shown gave the isomer ratios:

Elapsed Reaction Relative Relative Time (Hrs) Cis Trans 0 93.7 6.1 (0.5 to 1.0 min.) 45.7 54.3 0.88 18.8 81.2 5.25 7.4 92.6

EXAMPLE 24 One g of cis-A -pseudo ionone was isomerized to the trans-isomer by mixing with 1 drop of B1 etherate and allowing to stand at ambient temperature for 22.3 hours. Gas-liquid chromatographic analysis of samples taken at the elapsed reaction times shown had the following isomer ratios:

Elapsed Reaction Relative Relative Time (Hrs) Cis 7: Trans EXAMPLE 25 One g of cis-A -pseudo ionone was isomerized to the trans-isomer using 1 g of a solution of 1 g AgNO 4 g H 0 and 25 ml MeOH. The mixture was allowed to stand at ambient temperature for 21.8 hours. Gasliquid chromatographic analysis of samples taken at the elapsed reaction times shown below gave the isomer ratios:

Elapsed Reaction Relative Relative Time (Hrs) 71 Cis 7r Trans EXAMPLE 26 lsomerization of Cis-A -Pseudo lonone to Trans-A -Pseudo lonone and Cyclization to B-lonone and 22.5 g of acetic acid. After cooling to a 12C., the oil from step A was added dropwise, with stirring, over 1 hour at to 18C. The mixture was quenched 10 minutes after the addition was completed by pouring into 300 ml of H 0 and 50 ml of benzene, with stirring. The organic phase was separated, and washed with 40 ml of saturated aqueous Na CO solution in 100 ml of H 0, and then with a 50 ml portion of water. The solvent was removed under aspirator vacuum, and the oil produce flash-distilled at l to 2 mm Hg, 65 to 142C. head temperature, and 95 to 212C. pot temperature, to give 1 1.9 g of distillate and 1.2 g of residue. The direct yield of B-ionone was 43.2%, true yield 67.7%. Gas-liquid chromatographic analysis showed:

lsomerization of Cis-A -Pseudo lonone to Trans-A -Pseudo lonone and Cyclization to B-lonone A 5.0 portion of cis-A -pseudo ionone (83.7% cis- A ,8.3% trans-A was treated with 0.5 g of acetic acid at 95 to 120C. for 2.3 hours. A mixture of 17.5 g of 95% H 80, and 7 g acetic acid was cooled to 4C. and the above oil in acetic acid added dropwise over 47 minutes, at a temperature range between 4 and 18C., with stirring. The mixture was then poured into water and extracted with benzene. The benzene extracts were washed in succession with water, saturated aqueous sodium bicarbonate solution, and again water, prior to concentration under aspirator vacuum. Flash distillation of the remaining oil at 1.5 mm Hg, head temperature 30 to 122C., pot temperature 92 to 185C, gave 4.1 g of distillate containing 84.8% B-ionone. Yield 70%.

EXAMPLE 28 Into a metal pressure vessel equipped with a magnetic stirrer was combined 5.0 g of cis-pseudo ionone (77.4% A -cis, 22.6% A trans) and 95.0 g of toluene. The mixture was heated at 150C. for a total of 23.1 hours to give a mixture of 20.4% A -cis-pseudo ionone and 79.5% A-trans-pseudo ionone by gas-liquid chromatography.

EXAMPLE 29 To 3 g of Cu(BF in 14 ml hot methanol was added 12.1 g of triethylamine and the mixture stirred 18 hours at room temperature. The resulting precipitate was filtered and washed in succession with methanol and then ether. The solids were air dried to give 1.1 g of sky blue powder.

Dehydrolinalool (15.2 g) was combined with 21.4 g of Z-methoxy propene and 0.3 g of the above catalyst in a glass-lined pressure-resisting vessel. A magnetic stirring bar was added and the mixture heated at 90 with stirring for 17 hours. The brown turbid mixture was filtered and washed with water prior to removing lights under aspirator vacuum. Flash distillation of the remaining oil at 0.3 to 0.8 mm Hg, 35 to C. head temperature, 60 to 180C. pot temperature gave 17.2 g of distillate and 1.0 g of residue. The distillate as analyzed by gas-liquid chromatography container 1 1.1 g of dehydrolinalool, and 4.07 grams of condensation product.

Having regard to the foregoing disclosure, the following is claimed as the inventive and patentable embodiments thereof:

1. A process for preparing cis-A -pseudo ionones and cis-A -pseudo methyl ionones from dehydrolinalool and lower alkyl homologues thereof by condensation with an isopropenyl or isobutenyl lower alkyl ether, comprising condensing dehydrolinalool or a lower alkyl homologue thereof having the formula:

wherein R R R and R are hydrogen or lower alkyl having from one to about four carbon atoms and with an isopropenyl or isobutyl lower alkyl ether in the presence of a metal salt-amine complex catalyst of the formula:

wherein M is a metal selected. from the group consisting of copper, chromium and silver, Y is the anion of the salt and is selected from the group consisting of chloride, bromide, iodide, nitrate, and sulphate; x and z are integers selected according to the valence of M and Y, n is a number within the range from about 0.01 to about 50, and

I [11, N all is selected from the group consisting of aliphatic hydrocarbon amines, cycloaliphatic hydrocarbon amines, cy cloaliphatic aliphatic hydrocarbon amines, monocarbocyclic aromatic amines, and heterocyclic amines in which two or three of R R and R are taken together to form a heterocyclic ring, which may include nitrogen, oxygen, and sulfur hetero atoms; R,, R and R taken singly or together. being hydrocarbon groups having from one to about 30 carbon atoms or hydro- .gen, the condensation being carried out at a reaction temperature within the range from about 80 to about C, thereby obtaining a cis-A -pseudo ionone or a cis-A -pseudo methyl ionone.

2. A process according to claim 1, in which the reaction time is from 0.2 to about 72 hours.

3. A process according to claim 1, in which dehydrolinalool is condensed.

4. A process according to claim 1, in which dehydrolinalool is condensed with an isopropenyl ether to form pseudo ionone.

5. A process according to claim 1, in which dehydrolinalool is condensed with an isobutenyl ether to form iso and normal pseudo methyl ionone.

6. A process according to claim 1, in which the amount of catalyst is within the range from about 0.1 to about by weight of the reaction mixture.

7. A process according to claim 1, in which the reaction temperature is from 85 to 120C.

8. A process according to claim 1, in which the metal of the catalyst is copper.

9. A process according to claim 8, in which the metal of the catalyst is chromium.

10. A process according to claim 8, in which the metal of the catalyst is silver.

11. A process according to claim 1, in which the amine of the catalyst is an aliphatic amine.

12. A process according to claim 11, in which the amine is a primary amine.

13. A process according to claim 12, in which the amine is a secondary amine.

14. A process according to claim 12, in which the amine is a tertiary amine.

15. A process according to claim 1, in which the amine of the catlyst is an aromatic amine.

16. A process according to claim 1, in which the amine of the catalyst is a heterocyclic amine.

17. A process according to claim 1, in which M is copper, and

is an aliphatic hydrocarbon amine, wherein R R and R are monovalent hydrocarbon groups having from one to about thirty carbon atoms or hydrogen.

18. A process for preparing a,B-ethylenic ketones, which comprises condensing a tertiary acetylenic carbinol having the formula:

wherein a. R is selected from the group consisting of:

on, on,

wherein R R and R are selected from the group con- 6 sisting of hydrogen, lower alkyl and lower alkenyl having from one to about four carbon atoms;

b. R" is selected from the group consisting of lower alkyl and lower alkenyl having from one to about four carbon atoms; with an isopropenyl or isobutenyl lower alkyl ether in the presence ofa metal saltamine complex catalyst of the formula wherein M is a metal selected from the group consisting of copper, chromium and silver, Y is the anion of the salt and is selected from the group consisting of chloride, bromide, iodide, nitrate, and sulphate; x and z are integers selected according to the valence of M and Y, n is a number within the range from about 0.01 to about 50, and

R, l I

is selected from the group consisting of aliphatic hydrocarbon amines, cycloaliphatic hydrocarbon amines, cycloaliphatic aliphatic hydrocarbon amines, monocarbocyclic aromatic amines, and heterocyclic amines in which two or three of R R and R are taken together to form a heterocyclic ring, which may include nitrogen, oxygen, and sulfur hetero atoms; R,, R and R taken singly or together, being hydrocarbon groups having from one to about 30 carbon atoms or hydrogen, the condensation being carried out at a reaction temperature within the range from about to about C, thereby obtaining an a,B-ethylenic ketone.

19. A process according to claim 18 in which M is copper and 29 is an aliphatic hydrocarbon amine, wherein R R and R are monovalent hydrocarbon groups having from one to about 30 carbon atoms or hydrogen.

20. A process according to claim 18, in which R is wherein R R and R are selected from the group consisting of hydrogen, lower alkyl and lower alkenyl having from one to about four carbon atoms R" is lower alkyl.

21. A process according to claim 18, in which the reaction time is from 0.2 to about 72 hours.

22. A process according to claim 18, in which the amount of catalyst is within the range from about 0.l to about 10% by weight of the reaction mixture.

23. A process according to claim 18, in which the reaction temperature is from to C.

24. A process according to claim 18, in which the tertiary acetylenic carbinol is condensed with an isopropenyl lower alkyl ether.

25. A process according to claim 18, in which the tertiary acetylenic carbinol is condensed with an isobutenyl lower alkyl ether.

@395 UNITED STATEJ PA'IEN'I OFFICE ll/3L1] I '1 r 1 CERFIHCAFE 9F CORREC'HON Patent 1:0. 3.886.215 Dated m 27, 1.975

fls) Pobert S. DeSimone et 211 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 64 v after "corresponding" insert -pseudo- "1 Column 16, line 24 z (8-,B andy should be Column 18, line 43 "CR(NO .9H O" should be -Cr(NO 9H O-- Column 23, line 41 "methanl" should be --methanol-- Column 24, line 58 "150.0" should be 15.0"

Column 25, line 10 produce should be "product-- Column 26, line 5 I "container" should be --contained- ColumnZ'Y, line 31 'catlyst" should be catalyst Signed and Scaled this second Day of March 1976 v [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPatenls and Trademarks 

1. A PROCESS FOR PREPARING CIS$3-PSEUDO IONONES AND CIS-$3PSUEDO METHYL IONONES FROM DEHYDROLINALOOL AND LOWER ALKYL HOMOLOGUES THEREOF BY CONDENSATION WITH AN ISOPROPENYL OR ISOBUTENYL LOWER ALKYL ETHER, COMPRISING CONDENSING DEHYDROLINALOOL OR A LOWER ALKYL HOMOLOGUE THEREOF HAVING THE FORMULA:
 2. A process according to claim 1, in which the reaction time is from 0.2 to abouT 72 hours.
 3. A process according to claim 1, in which dehydrolinalool is condensed.
 4. A process according to claim 1, in which dehydrolinalool is condensed with an isopropenyl ether to form pseudo ionone.
 5. A process according to claim 1, in which dehydrolinalool is condensed with an isobutenyl ether to form iso and normal pseudo methyl ionone.
 6. A process according to claim 1, in which the amount of catalyst is within the range from about 0.1 to about 10% by weight of the reaction mixture.
 7. A process according to claim 1, in which the reaction temperature is from 85* to 120*C.
 8. A process according to claim 1, in which the metal of the catalyst is copper.
 9. A process according to claim 8, in which the metal of the catalyst is chromium.
 10. A process according to claim 8, in which the metal of the catalyst is silver.
 11. A process according to claim 1, in which the amine of the catalyst is an aliphatic amine.
 12. A process according to claim 11, in which the amine is a primary amine.
 13. A process according to claim 12, in which the amine is a secondary amine.
 14. A process according to claim 12, in which the amine is a tertiary amine.
 15. A process according to claim 1, in which the amine of the catlyst is an aromatic amine.
 16. A process according to claim 1, in which the amine of the catalyst is a heterocyclic amine.
 17. A process according to claim 1, in which M is copper, and
 18. A process for preparing Alpha , Beta -ethylenic ketones, which comprises condensing a tertiary acetylenic carbinol having the formula:
 19. A process according to claim 18 in which M is copper and
 20. A process according to claim 18, in which R'' is
 21. A process according to claim 18, in which the reaction time is from 0.2 to about 72 hours.
 22. A process according to claim 18, in which the amount of catalyst is within the range from about 0.1 to about 10% by weight of the reaction mixture.
 23. A process according to claim 18, in which the reaction temperature is from 85* to 120*C.
 24. A process according to claim 18, in which the tertiary acetylenic carbinol is condensed with an isopropenyl lower alkyl ether.
 25. A process according to claim 18, in which the tertiary acetylenic carbinol is condensed with an isobutenyl lower alkyl ether. 